JPS5951244A - 3-aminomethyl-1-(3-aminopropyl-1-methyl)-4-methylcyclohexane, manufacture and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel compounds, 3-aminomethyl-1-(6-
Amylagro Blue 1--Methyl)-4-methylcyclohexane, Process for its Preparation, Starting from limonene and/or its mono-hyP chloroformylation product - first obtaining the dihydroformylation product of limonene, then the present invention Novel Compound % 5-A-T-Methyl-1 of Method 1 for Obtaining the Compound and Method of Using the Present Compound as a Corrosion Inhibitor, Crosslinking Agent for Epoxy Resins and Chain Extender for Isocyanate Gleborimers -(3-amylafu-1-methyl)-4-methylcyclohexane can be characterized by the following formula.

In this specification, hereinafter, 1 the diamine of the present invention"
There are 18 types of diastereomers in the diamine of the present invention, which will be referred to as ``diastereomers'', and these are usually in the form of a mixture of all or some of the diastereomers. Each diastereomer is 1
From such a mixture, the usual diastereomer separation method,
g>ha, for example by capillary gas chromatography (capillary Go) or high pressure liquid chromatography (HPLO).
Shitashi can also be isolated.

The process of the present invention for the production of 3-aminomethyl-1-(5-aminoalrobyl-1-methyl)-4-methylcyclohexane comprises combining t-limonene and/or the monohydroformylation product of limonene with carbon monoxide and hydrogen, from 80 to With an excursion of 180 DEG C. and a pressure of 20 to 1.000 pars, a rhodium-containing catalyst 1, i.e. 1 rhodium, and further carbon monoxide, 2 to 1
Alkenes containing two carbon atoms and nitrogen to sulfur 1
Reacting in the presence of a catalyst containing at least one ligand selected from the group consisting of organic compounds containing rR or phosphorus in the presence of 1 to 1 f rhodium per starting material.
The sohydroformylation product of 14I talimonene is then characterized by treatment with hydrogen at 5°C to 150°C in the presence of ammonia and a hydrogenation catalyst.

In the production method of the present invention, limonene (4-isoglobylmethylcyclohexane) from any source can be used as needed. Limonene is present either in the form of a mixture of t-enantiomers, e.g.
, (+)-17monene or (B), ←)-limonene.

Limonene is, for example, a natural product 1, especially Kan 41i+'r'1
It can be obtained by extraction from 14 fruits and coniferous species.

Monohydroformylation products of limonene, e.g. jtJ
f4-Methylcyclohexa-6-nin-β-methylgropanal can also be used in the process of the present invention. Monohydroformylation products of limonene are known, for example, Kunio Kokami et al., Nippon Yuka Jizume U (6), 31
See page 6 (1973).

The monohydroformylation product of risonene can be used in the form of the reaction mixture obtained in the monohydrotetraformylation of limonene, preferably after separation of the catalyst used. The monohydroformylation product of limonene may also be used by distilling the monohydroformylation reaction mixture.

In addition, any mixture of limonene and a monohydroformylation product of limonene can be used in the process of the invention.

According to the invention, the reaction of limonene and/or the monohydroformylation product of limonene with carbon monoxide and hydrogen is carried out using a rhodium-containing catalyst 1, i.e. together with rhodium - carbon oxide, alkenes having from 2 to 12 carbon atoms. and at least one ligand selected from the group consisting of organic compounds containing nitrogen, sulfur, oxygen or phosphorous. The rhodium-containing catalyst is preferably one that dissolves in the reaction mixture. The rhodium-containing catalyst also contains several identical or different ligands as mentioned above, and also anionic groups, such as halogen atoms and/or acetate groups. Suitable ligands selected from the group consisting of alkenes having 2 to 12 carbon atoms, which can be acyclic, cyclic or bicyclic, containing one or more olefinic double bonds. can be included. The ligand preferably contains two olefinic double bonds, e.g. bicyclo[2+2.1] to but-1
, 4-diene and cycloocta-1,5-diene.

Examples of suitable ligands from the group consisting of nitrogen-containing organic compounds are amines, tertiary amines, especially aromatic and heterocyclic tertiary amines, are preferred examples, such as pyridine, picolines, ethyl Pyridines, N-methylvirolone,
N-Methylvirol, N,N'-trimethylpiperazine, 1methylcyclohexylamine, triethylamine, N,N-dimethylaniline, 1N-methylmorpholine%
N-methylindole, quinoline to isoquinoline and N
-Methylpyrrolidone may be mentioned.

Examples of suitable ligands from the group consisting of sulfur-containing compounds are organic disulfides and sulfoxides. Examples include sopendylsulfide, di-n-butylsulfide, dimethylsulfoxide, soethylsulfoxide, Di(4-chloropentyl) sulfide, Di(4-cyanobenzyl) sulfide, Bis(4-dimethylaminopentyl) sulfide, Di(4-diethylaminobenzyl) sulfide, Di(α-naphthylmethyl) sulfide, Di(2, 6-dichloropenzyl) sulfide,
di(3,4-dichlorobenzyl) sulfide, so(
2-chlorobenzyl) sulfidoruso (5,6,7,
8-tetrahydronaphth-2-ylmethyl) sulfide, benzylmethyl sulfide, benzyldodecyl sulfide, 4-dimethylaminobenzylmethyl sulfide,
Benzylbutyl sulfide, bis-(4-carboxypentyl) sulfide,
Mention may be made of ci-(4-methylbenzyl) sulfide, ci-(3-methylpenzyl) sulfide and di-(2-methylbenzyl) sulfide.

Examples of suitable ligands from the group consisting of organic compounds containing enzymes are unsubstituted and substituted acetylacetonates. Substituted acetylacetonates include - for example - alkyl, phenyl, substituted phenyl, and/or hafluoroalkyl groups. Examples of ligands from the group consisting of oxygen-containing organic compounds include trifluoropenta-2,4-dione, 1-benzoylacetone and 2-acetylcyclopentanone.

Suitable ligands from the group consisting of phosphorus-containing organic compounds are:
An example is the triorganophosphorus ligand. In the tertiary modal phosphine and subh'F Ctj2 esters, one same or different alkyl group having from 1 to 201 carbon atoms;
cycloalkyl group having 5 to 12 carbon atoms, 7 to
Particular preference is given to containing an aralkyl group having 10 carbon atoms and at least one aryl group having 3 to 7 carbon atoms.

These alkyl, cycloalkyl) aralkyl and aryl groups have S substituents, such as 1 to 6 hydroxyl groups, 1 to 6 hydroxyl groups,
alkoxy and/or carbalkoxy groups having 4 carbon atoms, an optionally truncated amino group and/or
Or, even if it has a nodoroquine atom, the fj11 position from the group consisting of organic compounds containing su is 1.
('Ini triphenylphosphine, soethylphenylphosphine, tritolylbosphine-trinaphthylphosphine, sophenylmethylphosphine, dinoenylbutylphosphine, tris-CP-10 lophenyl)
Phosphine, tris-(p-carbomethoxyphenyl)
Phosphine, tris-(p-7anophenyl)phosphine, sophenylphosphone 11 (phenyl ester, benzene phosphonite diphenyl ester, '4'a 1'c2) liphenyl ester, P[0H2CH,0
11tN((14,), ], p(aH,aH2an,
ti (c2u,), ), ,p(○H,OH,0H2
-N)]-]1eo-0. H,3,P['OH,OH,
0H2N(iso-CaHe)*)s, (n-04H,
)2POH,OfI,N(0,H,),,P L (j
HtN(Ox H5)2 Js,P [06H,N
(OH,)2)iP [O)l, OH! To OR2 (
ter t , 04H1+)2) S and P (OH2
01f20 H2N (is o -Os H?)
t]S.

Among the tertiary organic phosphines and phosphorous esters, triarylphosphines and phosphorous triaryl esters/)'JlfJL, i.

Other suitable ligands from the group consisting of phosphorus-containing organic compounds include complex ligands consisting of triorganophosphinepox 1, partially HL substituted with +41S with ferrocene, for which: For example, the country of Germany'IjWF
It is described in Publication No. 2,61, No. 306.

Preferred rhodium-containing catalysts for the process of the invention have the formula:
Rh(00)L,,XRlx(Co)L,,RhXL3
, [“h(C0)2”t)! and [Rh(OCOCH3
)(00)L].

or represents a chlorine, bromine or iodine atom, and L represents one of the above-mentioned ligands.

Particularly preferable lotium-containing WP+ for the method of the invention
II mediumtit%2! , rhodium-carbonyl-chloride, Rh, (0,1(,ri, C12, kth(
Co), acac.

”[[(CHsHs)zFθ)PPh,), 01., R
h[(Caday, 1CHt)tS]5C1s, f(h(1
'Ph, ), OX, Rh (PPh3), Br, Rh (
PPh, ), ('l,, 2-ethylhexane 1 tube rhodium, Rh [(4-OH, O(!, H40) 1.), S]
, C1,, R11 [4-010, H40) 12) 28]
301. , Rh[a,)1. OH,), So 3. al
, and Rh[(OH,), 80J, 01. .

1 in the formula acat4; represents I acetylacetonato group, and The hills contain phenyl groups, It is.

Rhodium content power 11 mentioned above! Media 11 In the method of the present invention, there is no core used in the form of a complex. It is also possible to add the rhodium salt and one or more ligands separately to the manufacturing process of the invention, advantageously eliminating the need for a separate preparation of the rhodium complex compound. Furthermore, it is generally possible to replace some of the rhodium with cobalt, i
- up to 95% by weight of the rhodium, preferably up to 90% by weight of the rhodium, can be replaced by cobalt.

According to the present invention, the rhodium-containing catalyst is used in an amount corresponding to 11 or less rhodium metal per IKp of monolimonene and/or monohyloformylation product of limonene (i.e. starting material). 1Kf of substance
The hydroformylation according to the invention, in which from 1 to 1.000 to 1%, preferably from 10 to 600%, per 10 dium metal is used, is especially carried out in the liquid phase. Rhodium-containing %li media can also be used, for example, by P. Eng., Davia+3on et al.
is.

Volume 1 (1976)! It may be supported on a solid carrier as described on pages 191-395.

In most single cases, the liquid phase contains the starting materials, reaction products +
1', J and rhodium-containing S I:mt medium. However, the reaction is also substantially inert under one or more inert or reaction conditions, and the rhodium-containing f81! Suitable diluents, which can be carried out in the presence of a solvent capable of decomposing the medium, include, for example, alkyl-substituted benzenes; high-boiling esters, such as dicarboxylic acid alkyl esters; esters of polyols, such as trimethylol. High boiling ketones; high boiling alcohols such as butanol; high 73 point ethers and high boiling hydrocarbons such as saturated aliphatic and alicyclic hydrocarbons. It is also advantageous for hydrogen treatment in the presence of ammonia, which is carried out in the presence of ammonia, and preferable examples of these solvents include benzene, toluene, xylene, isofuronosonol, methylcyclohexane, decali/, Mention may be made of dioxane 1 tetrahydrofuran, ethylene glycol monoethyl ether and diethylene glycol methyl ether.

In the reaction of limonene and/or the monohydroformylation product of limonene with carbon monoxide and hydrogen according to the invention, the -carbon and hydrogen oxides generally react at least theoretically with the dinohydroformylation product of limonene. 10 to
Only a certain amount of core wire is used to make the zero section. - Carbon and hydrogen oxides are preferably used in excess, for example up to 1 mole DO, O in each case. - Carbon oxide and hydrogen can both be used in various proportions. For example, the volume ratio of carbon oxide to hydrogen is from 4:1 to 1=4 (l), preferably carbon oxide and hydrogen are used in approximately the same volume amount.

The reaction of limonene and/or the monohydroformylation product of limonene with carbon oxide and hydrogen according to the invention is carried out in a mud bed at 80-180° C. under a royal power of 20-1.000 par. . Preferably the temperature is in the range 105°C to 180°C and the pressure in the range 100 to 400 bar.

A fhA degree range of 120°C to 170°C is particularly preferred,
Hydroformylation is carried out stepwise, i.e. at first
^Ha For example, at 80 to 140℃, then at a high temperature, for example 1
It may be advantageous to ripen the fruit at 30-180°C. It can also be advantageously carried out to add the catalyst -BII, the thickener and/or the starting materials only during the reaction.

The reaction mixture obtained by the reaction of limonene and/or the monohydroformylation product of limonene with carbon monoxide and hydrogen according to the invention can be treated directly with hydrogen in the presence of ammonia (reductive amination). . This is advantageous from an economic point of view, especially since there is no need to separate the lotium-containing catalyst, 1 which can be expensive to separate very small amounts of catalyst. However, if the catalyst is removed from the reaction mixture,
It is also possible to separate the sohydroformylation product of limonene from the reaction product, for example by distillation or extraction, and to reuse it if appropriate. The still existing monohydroformylation product which can be separated and used advantageously only this product in a subsequent reductive amination can likewise be separated by distillation;
If appropriate, it can be fed fresh again to the reaction with carbon monoxide and hydrogen.

The reductive amination according to the invention is generally carried out in the presence of at least 2 moles of ammonia per mole of limonene dihydroformylation product.

Preferably, an excess of ammonia is used, for example from 3 to 20 moles of ammonia per mole of sohydroformylation product of limonene.

The stock amination according to the invention is carried out in the presence of a hydrogenation catalyst. Suitable catalysts are, for example, those containing as active component one or more elements with atomic threat numbers 23 to 29 in the form of metals and/or oxides.

Examples of suitable catalysts include ~nickel or cobalt catalysts, such as supported nickel.

Here, the carrier is an inorganic substance such as diatomaceous earth, silicic acid,
Aluminum oxide, silicate, aluminum silicate 1 Montmorillonite - zeolite, spinel - dolomite - kaolin 1 Magnesium silicate, zirconium oxide % iron oxide 1 zinc oxide, calcium carbonate - silicon carbide, 1N
ff aluminum monophosphate, asbestos or activated carbon, and high molecular weight natural or synthetic organic materials such as polyamino polystyrene, cellulose or polyurethane are used. The carrier can be, for example, in the form of beads, strings, fibers, cylinders or polygons, or in the form of a powder.

Other suitable catalysts include Raney type catalysts, such as Raney nickel, W-1-1W-5-1V/-6- and w
-7-Raney nickel (H.

Adkins, J. Am, Ohem, Sac, 6950
39 (1974)), Raney cobalt catalyst, Raney copper,
Metal catalysts prepared by 34 elements of Raney nickel/iron, Raney cobalt/nickel and Raney cobalt/iron, nickel salts or cobalt salts, such as urushihara nickel, nickel salts or cobalt salts reduced with metal alkyl compounds 1. Catalysts made by alkali gold A4 hydride, hydrazino, boronate or water accumulated horon, metal oxide or gold JARide mixture) and gold lAr5Jl
The reduction of metal oxides or metal salts in which there may be compounds or mixtures of compounds may also be carried out using hydrogen, if appropriate at elevated temperatures and pressures, under the conditions of the process or during the performance of the process. It is done.

The catalyst may contain one or more of the following elements - Li
, Ha, Ca%Ba, K, Ag%I3e.

La, Oe%Ti, V%Nb, Ta, Mo, and W at 1
up to 0 ft%, and Ru, Rh, Pd, Au.

Up to 1% of PT and PT can be included as accelerators.

Particularly preferred hydrogenation catalysts are Raney catalysts such as Raney nickel-Raney cobalt and Raney nickel/iron - α01 to 10 w/h hydrogenation catalysts are commonly used.

Preferably %a1 to 5% by weight of hydrogenation catalyst is used.

The reductive amination according to the invention is carried out at 50-150°C. A temperature of 90-135°C is preferred.

Hydrogen pressure during amination should generally be greater than 10 pars. A hydrogen pressure of 50 to 200 bar is preferred.

Reductive amination according to the invention can be carried out in the presence or absence of a solvent. Suitable solvents are those mentioned above. The reaction mixture can also be diluted with the amine of the invention. The reaction is preferably carried out in such a way that the weight ratio of sohydroformylation product to agent 64 is 1=1. It is carried out at a ratio of 5 to 3:1.

Reductive amination according to the invention can be carried out in continuous mode or in patch mode.

It is advantageous to first separate the free water from the dihydroformylation product of limonene and the ammonia, optionally in the presence of a solvent, to form the 8chiff base, followed by hydrogen treatment. It can be. Furthermore, hydrogen M1t1M, ammonia and the bath agent or diamine according to the invention already prepared are introduced into the autoclave under hydrogen pressure and in one pump the sohydroformylation product of limonene is fed with one pump or, if necessary, a solvent. It may be advantageous to do so. Finally, it is also advantageous to carry out the reductive amination according to the invention with the addition of an acid with a catalytic power of 1%.

As acids, inorganic acids, such as phosphoric acid, or organic acids, such as acetic acid, propionic acid or cono-phosphoric acid, can be used. The amount of acid added is preferably 0.1 to 3% by weight based on the sono-hydroformylated product used. 90-99% of the dialdehyde is converted to the diamine of the present invention. If pure or substantially pure limonenedialdehyde is used in the primary amination, a sufficiently pure diamine according to the invention can be
After reductive amination, the hydrogenation (8J) release can be obtained by filtration or centrifugation near f# and, if necessary, by simply separating the solvent. In other cases 1, especially if the crude dihydroformylation product of limonene is used in a reductive amination, 1 the reaction mixture is generally subjected to hydrogen-catalyzed separation ρ
In order to obtain sufficiently pure diamines according to the invention, a subsequent treatment, for example by distillation or decomposition, is necessary.

As mentioned above, one diamine Oj according to the invention is generally obtained as a mixture of several or all of the enantiomers. The composition of this mixture depends, inter alia, on the starting materials.

Especially R(+)-limonene%S(+)-limonene, d7-
It depends on whether limonene or a mixture of these limonene enantiomers is used.

Furthermore, the present invention provides %3-aminomethyl=1-(3-7minoglobyl-1-methyl)-4-methylcyclohexane,
Corrosion inhibitor, cross-linked h'Js and IJ for epoxy resins
Chain Length for CO Prepolymers The present invention relates to methods of use as e.g. used in the production of polyurethane-polyureas. The diamines according to the invention have an excellent affinity with hydrocarbon-based heating oils, lubricants and liquid blowing agents and therefore have a high affinity for such materials.
As a corrosion inhibitor, for example, 0.01 to 1 weight lj::%
tK'g can be added. If the diamine according to the invention is used as a crosslinking agent for epoxy resins and as a chain extender for NCo prepolymers, it is no different than when other diamines are used for this purpose. The same amount is added. The type of diastereomeric mixture of diamines according to the invention is not critical for these applications.

The present invention provides for the first time an industrially interesting diamine that can be synthesized from a renewable raw material, limonene.

According to the present invention, 5-aminomethyl-1 from limonene
-(3-Aminozorobyl-i-methyl)-4-methyl-
The fact that cyclohexane can be obtained in good yield is truly remarkable.

Lake 1 Japan Oil Chemistry Journal% 22 (6) 316 (197
In 3), the method of hydroformylation of limonene is described, in which 4-methylcyclohex-3-ene-
β-Methylpropanol (i.e., the monohydropormylation product of limonene) is obtained in 45-52% yield) and dihydroformylation product is obtained in up to 16% yield using cobalt carbonyl as catalyst. It states that it can be obtained at a rate. In the same manner, using rhodium monochloride trihydrate as a catalyst, 1.7 Y as rhodium per 1 Kf of limonene was added.
When using f equivalent 91, the yield of the sohydroformylation product of limonene obtained is only 2-7%.

Useful for hydroformylation of limonene in various bath additives.
Ind+Kng, Ohem, Proc.

81 published in Res, Dev, 4 283 (1965). What is obtained is always a mixture of monohydroformylated products with very little sohydroformylated product.

European Mother ""J' fFl 1nu: 1 Publication No. 54.
In No. 986, 4-)
An improved synthesis method for menalgropanol was presented. There is no mention of whether ld or fl'l should be used.

K., FalbG, - New synthesis using carbonated carbonate (Syn
theses with Oa, rbon
, Monoxide.

Springer-Varlag Heidelbe
rg.

do not have.

These prior art and intermediate stages of limonene to limonene sohydroformyl products
During the synthesis of this diamine, FJ',
s'j) Also for Kaku) Technique 1, There is a big gap in I, limonene's dinoidroformyl metamorphosis hl',
References in the literature above include monobu', 71i', l, and less modification of rhodium carp! Using I'4', 75
I was defeated by a high selection rate, part 1. Therefore, it is completely impossible to predict that the diamine of the present invention could be obtained with an 11 content of 90% or more.

Examples Example 1 100F limonene monoaldehyde (4-methylcyclohex-3-ene-β-methylglocknol), 30
0+++/cyclohexane and 012 divalent rhodium carbonyl chloride) Company 70OrnI! into a stainless steel autoclave and water gas (OO/H).
2) Press down 5117 and heat to 145°C. The pressure is
200 to 220 while periodically supplying and discharging water gas to the
Keep it pearly. For 2 hours (), the pressure remains constant at 1ζA
The autoclave is cooled down to 1%, and the reaction mixture is separated into its components by thin film distillation.
4-Methyl-5-formylcyclohecan-β-methylpropatool) was obtained, corresponding to a selectivity of 75%. Infrared j″-spectrum twr −′):
2.920.2.720.1, 725.1.450.1
, 380mb) reductive amination of 155f limonenedialdehyde (4-methyl-3-formylcyclohexane-β-methylglopanol), 3
00m1! of tetrahydrofuran and 10'I of Raney nickel ffi 1. First, it is introduced into a stainless steel autoclave of s1 and stirred.

300°C of liquid ammonia was injected and the mixture was heated to 100°C.
7. Keep at this temperature for 1 hour. Then, 1
Hydrogenation was carried out at 20°C and a total pressure of 140 par. The pressure was maintained at 140 par by periodically injecting hydrogen. 1 pressure became constant after 5 hours. The autoclave was cooled, the pressure was released, the catalyst was separated, and the reaction mixture was distilled to separate its components. 117f of 6-aminomethyl-1-(3-aminopropyl-1-methyl)-4-methylcyclohexane is obtained at a boiling point of 147 DEG -156 DEG C. and .alpha.05 mbar, corresponding to a selectivity of 87. The resulting pupil of So-Amin was determined by titration with 1N hydrochloric acid and was found to be 10 [L2f1 mol (il
car fit * 99t 1 mol). Infrared spectrum (cm-'): 3,300.2.900.1.
600.1,450.1,380% 830° Example
2 600 F limonene, 150 me cyclohexane and 0.6 g Rh2(CaH+ 2 )2C12 in 1
．． 6 was heated to 150°C under water gas pressure (jl・1) in a stainless steel autoclave. After the reaction was completed, the autoclave was cooled down, and the reaction mixture was separated into its respective components by distillation. A small amount of monoaldehyde was obtained at a boiling point of 90° C. This was further hydroformylated according to Example 1a. The obtained dualdehyde (boiling point, 150°C, 10.0
Example 6 2501 of limonene monoaldehyde, 750 mg of toluene, and cL25F's "CCC5Hs)tFe3'I"
PPh2], 01. in a stainless steel autoclave with a capacity of 1.6 t).
i) The mixture was heated to 145° C. for 1 hour under reduced pressure and stirring. The pressure is 1 and 12 while periodically injecting water gas.
Maintained between 50 and 280 bar. After 2 hours, the pressure remained constant and the autoclave was cooled down to 10°C.

Analysis of the product by chromatography revealed that the content of 1-dialdehyde was 21%, corresponding to a yield of 70% and a selectivity of 81%.

Continuation of page 1 0 shots clearer Rudolf Braden Federal Republic of Germany Day 5068 Puntar Notehausale Elt 1

Claims (1)

[Claims] 1.3-aminomethyl-1-(3-aminopropyl-1
-methyl)-4-methylcyclohexane. 2. Limonene and/or a monohydroformylation product of limonene with carbon oxide and hydrogen, 80 to 18
Consisting of 10 soum plus 1 additional carbon monoxide, alkenes with 2 to 12 carbon atoms and organic compounds containing nitrogen, sulfur, oxygen or states under a pressure of 20 to 1000 par at a temperature of 0 ° C. 1 rhodium per Kf of limonene or limonene monohydroformylation product of a rhodium-containing catalyst containing at least one ligand selected from the group
in the presence of an amount corresponding to or less than
Thereby forming a sohydroformylation product of slimonene, followed by partial amination by contacting the sohydropormylation product of t-limonene with hydrogen at 50-150'C in the presence of ammonia and a hydrogenation catalyst. A patented method for producing 5-aminomethyl-1-(3-aminopropyl-1-methyl)-4-methyl-cyclohexane. (5) Alkenes, tertiary amines, sosulfides, sulfoxides, and acetylacetonates in which the rhodium-containing catalyst has 10 dium, 12 to 12 carbon atoms and 2 olefin double bonds, tertiary amines, sosulfides, and sulfoxides , 5th-class organic phosphines, and 1 patent claim 2 characterized by
Manufacturing method described in section 4. Is the rhodium-containing catalyst trimerized rhodium-cal 4?
Niluchloride, Rht (Cs “1t)t C1
2, Rh(Co), acac, Rh[(0,H,
OH,), 83. C1,,Rh(PPh,),01,R
h[(c,H,),pθ]PPh,)301. , Rh(
PPh, )sBr, Rh(PPh, ), 01. ．． Rhosium 2-ethylhexanoate, Rh[(4-OH8O-06
H,○"t)t"']501s % Rh[(4-01
-c6H4cu, ), s), cx3, Rh [' (
06H,OH2)2EIO), (31° and Rh[(O
3. The method according to claim 2, wherein acac represents an acetylacetonato group, and ph represents a phenyl group. 5. The rhodium-containing catalyst is 1 Kt of starting material, 1
The manufacturing method according to claim 2, characterized in that an amount corresponding to 0 to 60 cm is used. 5 - Reaction with carbon oxide and hydrogen and reductive amination,
The manufacturing method according to claim 2, characterized in that the reaction with Z-carbon oxide and hydrogen is carried out in the presence of an fd agent at a temperature of -100 to 400°C.
The manufacturing method according to claim 2, characterized in that the manufacturing method is carried out under pressure of pearls. a Reductive amination as an active ingredient, atomic number 923 ~
% characterized in that it is carried out in the presence of a catalyst containing one type of 290 elements or 2fi11 or more in the form of one metal or oxide.
l:! Sieve/'I'Claim No. 2'' (4, 1l-15
9. Dihydroformylation product of Limo 51.
Treatment with hydrogen in the presence of ammonia
3. Process according to claim 2, characterized in that it is carried out at 5[deg.] C. and under a pressure of 50 to 200 bar. 1.alpha. The rhodium-containing catalyst is characterized in that the rhodium bipod is nyl chloride. 1. Required Scope No. 21) JII's proprietary manufacturing method. 11. The hydrogenation catalyst is Raney nickel. 12. The production method according to claim 2, characterized in that the rhodium catalyst is a mixture with a cobalt-containing catalyst. Method. 15. The production method according to item 2, characterized in that the ligand is a triorganophosphine. 15. The manufacturing method according to claim 2, wherein the ligand is triarylphosphine. 16. The production method according to claim 2, characterized in that the ligand is a phosphorous acid triaryl ester. 17. Hydrocarbon and 3-aminomethyl-1-(3-aminopropyl- 1-Methyl)-4-methylcyclohexane.